EP1110976A1 - Partially crystalline propylene polymer compositions having an improved suitability for the preparation of biaxially oriented films - Google Patents
Partially crystalline propylene polymer compositions having an improved suitability for the preparation of biaxially oriented films Download PDFInfo
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- EP1110976A1 EP1110976A1 EP00127654A EP00127654A EP1110976A1 EP 1110976 A1 EP1110976 A1 EP 1110976A1 EP 00127654 A EP00127654 A EP 00127654A EP 00127654 A EP00127654 A EP 00127654A EP 1110976 A1 EP1110976 A1 EP 1110976A1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F10/06—Propene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F110/06—Propene
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/06—Propene
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/90—Direct application of fluid pressure differential to shape, reshape, i.e. distort, or sustain an article or preform and heat-setting, i.e. crystallizing of stretched or molecularly oriented portion thereof
- Y10S264/901—Heat-setting of stretched or molecularly oriented article formed from planar preform, e.g. sheet, film
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/91—Product with molecular orientation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen
Definitions
- the present invention relates to partially crystalline propylene polymer compositions, which are particularly suitable for Have production of biaxially oriented films. Moreover the invention relates to the use of the partially crystalline propylene polymer compositions for the production of foils, Fibers and moldings and the films, fibers and moldings from these compositions.
- polypropylene Understood a variety of different polymers, all of them have in common that they are to a large extent from the monomer Propylene were built.
- the different polypropylenes are usually achieved through coordinative polymerization on catalysts obtained from transition metals, which predominantly the monomers built into a growing polymer chain.
- the coordination catalysts are the propylene monomers not install absolutely uniformly, some monomers insert differently than the majority of the others, show the educated Polymer chains compared to the prevailing arrangement in each case "Error" on. The number can vary considerably.
- the polypropylenes are called atactic. These are completely amorphous and therefore have no melting point.
- polypropylene is currently mostly used heterogeneous catalysts based on titanium, wherein a predominantly isotactic polymer is produced.
- This Catalysts for which the name Ziegler-Natta catalysts naturalized, have several different polymerization active Centers on. The centers differed both in their stereospecificity, i.e. in how many "mistakes" the resulting chains, as well as how high the average molecular weight of the chains formed. As predominant Errors are observed in each case, i.e. individual propylene monomers were built in syndiospecific instead of isospecific.
- the result of the polymerization with such heterogeneous So catalysts is a mixture of different polymer chains, which differ both in their stereochemistry and in their molecular weight differentiate.
- An essential area of application for polypropylenes is foils, especially biaxially stretched films, which are often called BOPP - ("Biaxially Oriented Polypropylene -”) films.
- EP-A 339 804 describes a mixture of a homopolypropylene and a statistical propylene copolymer, wherein the comonomer in the upper range of the molecular weight distribution the mixture is built in. Such mixtures have good optical properties and mechanical properties, but are processable limited.
- EP-A 115 940 discloses for the production of biaxially stretched Suitable propylene-ethylene copolymers with 0.1 to 2.0 mol% ethylene and high isotacticity. These polymers have good elasticity, rigidity, transparency, Impact resistance and heat shrink resistance. However, it is enough they in their mechanical, rheological and optical properties often not yet meet the requirements of the manufacturers of BOPP films.
- EP-A 657 476 describes an ⁇ -olefin polymer obtained by polymerizing an ⁇ -olefin with 3 or more carbon atoms, whose composition is based on the proportions by weight 20 ° C soluble in xylene and insoluble at 105 ° C in xylene Shares is defined.
- JP-A 10 053 675 describes a polypropylene composition described, consisting of a high molecular weight crystalline Polypropylene with a soluble content of less than 5% and a low molecular weight polyolefin mass with a soluble Share of more than 30%.
- the propylene polymer compositions known from the prior art enable the production of biaxial oriented polypropylene films, however, they do not show at the same time optimal processability and very good mechanical Properties of the films. This means that it has not so far managed to reverse the relationship between processability and decouple mechanical properties of the foils.
- the present invention was therefore based on the object of propylene polymer compositions to develop that at the same time excellent processability to biaxially stretched films have and from which films with very good mechanical and have optical properties manufactured. Furthermore, should accessible with the least possible complex process and the films should have a good barrier effect, for example against oxygen and water vapor.
- a TREF Temporal Rising Elution Fractionation
- the partially crystalline propylene polymer compositions according to the invention are prepared by polymerizing propylene, ethylene and / or C 4 -C 18 -alk-1-enes.
- C 4 -C 18 alk-1-enes is understood to mean linear or branched alk-1-enes which have from four to eighteen carbon atoms. Linear alk-1-enes are preferred.
- Ethylene, but-1-ene, pent-1-ene, hex-1-ene, hept-1-ene or oct-1-ene or mixtures of these comonomers may be mentioned, preference being given to ethylene or but-1-ene is used.
- the propylene polymer compositions contain at least 50 mol% of monomer units which are formed by polymerizing propylene.
- the content of monomer units derived from propylene is preferably at least 70 mol% and in particular at least 85 mol%.
- propylene is used as the only monomer in the preparation of the propylene polymer compositions according to the invention, ie it is a propylene homopolymer. If one or more comonomers were used, it may be that the entire propylene polymer composition has an essentially identical comonomer distribution in the sense of statistical copolymers. However, it may also be the case that, like the so-called propylene impact copolymers, it is a mixture of different components which have different comonomer contents.
- the partially crystalline propylene polymer compositions according to the invention have a melting temperature T M which is in the range from 65 ° C. to 170 ° C. and preferably in the range from 135 ° C. to 165 ° C.
- the melting temperature T M is to be understood here as the temperature at which the enthalpy versus temperature curve obtained by differential scanning calorimetry (DSC) in accordance with ISO standard 3146 by heating at a heating rate of 20 ° C./min of a previously melted sample Maximum.
- the DSC measurement is usually carried out by first heating the sample at a heating rate of 20 ° C./min to about 40 ° C. above the melting temperature, then dynamically crystallizing the sample at a cooling rate of 20 ° C./min and with a second heating with a heating rate of 20 ° C / min the melting temperature T M is determined.
- GPC and TREF are methods that are used to measure polymer samples different physical properties can be separated can. While the GPC fractionates polymer chains based on their size, the TREF separates according to the crystallizability of the polymer molecules.
- the principle of "Temperature rising elution fractionation" has been detailed, for example by L. Wild, Advances in Polymer Sciences 98, 1-47 (1990) described. This is a polymer sample at an elevated temperature dissolved in a solvent, the concentration of Solution should be less than 2 wt .-%. The polymer solution will now cooled very slowly (approx. 0.1 ° C / min). First they fall Polymer molecules that crystallize very well and later molecules with poorer crystallization properties.
- This consists of a temperature-controlled storage vessel (1), a temperature-controlled one Elution vessel (2), two thermostats (3) (for example Type HC5 from Julabo), two temperature sensors (4) and a powerful mixer (5) with which the polymer suspension is mixed.
- a temperature-controlled storage vessel (1) a temperature-controlled one Elution vessel (2)
- two thermostats (3) for example Type HC5 from Julabo
- two temperature sensors (4) for example Type HC5 from Julabo
- a powerful mixer (5) with which the polymer suspension is mixed.
- the polymer sample is used for dissolution together with the Solvent in a glass jar with magnetic stir bar and attached Given a reflux condenser and then the glass vessel in one Tempering bath with stirring until the Polymers heated.
- the polymer solution is then e.g. by Lowering the glass vessel into the preheated oil bath of a thermostat, with a cooling rate of 10 ° C / h to room temperature chilled.
- the defined cooling can be done by the corresponding one Programming a programmer connected to the thermostat to reach.
- Usually 5 g for each TREF analysis Propylene polymer dissolved in 400 ml xylene.
- the polymer suspension resulting from the defined crystallization is transferred into the elution vessel (2) of the apparatus shown in FIG. 1, the temperature is heated to (T M / 2) + 7.5 ° C. and the polymer crystals at this temperature with vigorous mixing for 15 minutes extracted. The polymer solution is then drained off while the crystals remain in the extractor. The dissolved polymer is preferably precipitated in cold acetone (temperature ⁇ 0 ° C), filtered off and dried in vacuo at 100 ° C for 4 to 5 hours.
- the dissolved polymers of the individual fractions are preferred precipitated in cold acetone (temperature ⁇ 0 ° C), filtered off and Dried in vacuo for 4 to 5 hours at 100 ° C.
- the fractions can now be the individual components A, B and C. assign.
- the main component A is formed by all fractions to be taken into account, which are eluted at a temperature above (T M / 2) + 7.5 ° C and an average molecular weight M n (number average) ⁇ 120,000 g / mol.
- the secondary component B is formed by the fraction which is eluted at the temperature (T M / 2) + 7.5 ° C. If the proportion of the fraction eluted at the temperature (T M / 2) + 7.5 ° C. in the total propylene polymer composition is less than 1% by weight, the proportion of secondary component B according to the definition given above is the one to be taken into account Fractions equal to 0% by weight.
- the secondary component C is formed by all fractions to be taken into account, which are eluted at a temperature above (T M / 2) + 7.5 ° C and an average molecular weight Mn (number average) ⁇ 120,000 g / mol.
- Propylene polymer compositions is that at room temperature in xylene soluble portion XL, below that by a process to understand certain proportions analogous to ISO standard 1873-1: 1991 is. 5 g of polypropylene are distilled in 500 ml Xylene, which was previously heated to 100 ° C, added. Subsequently the mixture is heated to the boiling point of the xylene and held 60 min at this temperature. Then within 20 min cooled to 5 ° C with a cold bath and then back to 20 ° C warmed up. This temperature is held for 30 minutes. The fancy Polymer is filtered off. The filtrate will be exact 100 ml filled and the solvent on a rotary evaporator away. The remaining residue is left for about 2 h 80 ° C / 250 mbar dried to constant weight and after Cold balanced.
- the partially crystalline propylene polymer compositions according to This embodiment therefore has a broad molar mass distribution of the highly isotactic components. You are characterized by it from that compared to conventional, for the production of BOPP films Polypropylenes used, for example, improved mechanical Properties of the films and improved barrier properties can be achieved without there being disadvantages in processability gives.
- the semicrystalline propylene polymer compositions according to this embodiment have a relatively high content of low-tactical fractions which, however, are not soluble in xylene at a temperature (T M / 2) + 7.5 ° C. and low fractions soluble in xylene at room temperature. They are characterized in that they have improved processability compared to conventional polypropylenes used for the production of BOPP films, which is reflected in a widened temperature processing window and a widened speed processing window, and the optical properties of the films are improved without disadvantages in the mechanical properties of the films occur.
- the propylene polymer compositions are preferred but not polymerized separately. There is a possibility then in that a mixture of two or more different ones Catalysts are used that are set under the Polymerization conditions different polypropylenes deliver, or a catalyst is used by itself has such different active centers that he as such provides appropriate mixtures of polymer chains. Another Possibility is in so different conditions in different Reactors, for example a reactor cascade that ultimately polymerize to the desired composition results.
- the preparation of the components of the propylene polymer composition according to the invention or the entire propylene polymer composition can in a known manner in bulk, in suspension or in the gas phase in the usual, for the polymerization of reactors used either batchwise or preferably continuously, in one or more stages.
- the polymerizations are usually carried out at temperatures in the range of 20 to 150 ° C and pressures in the range of 1 to 100 bar with medium Residence times of 0.5 to 5 hours.
- Ziegler-Natta catalyst systems are used. These consist of usually from a titanium-containing solid component, for the In addition to titanium compounds, they are often also inorganic or polymeric particulate carriers, compounds of magnesium, halogen compounds and electron donor compounds used and at least one cocatalyst. As cocatalysts aluminum compounds come into consideration. Preferably be in addition to an aluminum compound as further cocatalysts one or more electron donor compounds are used.
- Catalyst systems can also be used to prepare the propylene polymers based on metallocene compounds.
- Complex compounds of metals are said to be here under metallocenes of subgroups of the periodic table with organic ligands are understood that together with metallocenium ion-forming Compounds yield effective catalyst systems.
- metallocenes contain as central atoms Titanium, hafnium or preferably zirconium, which generally is Central atom via a ⁇ bond to at least one, usually substituted cyclopentadienyl group is bound.
- the metallocene complexes are often supported in the catalyst systems in front.
- the metallocene catalyst systems also contain as Metallocenium ion-forming compounds, usually alumoxane compounds or strong, neutral Lewis acids, ionic Compounds with Lewis Acidic Cations or Ionic Compounds with Brönsted acids as a cation.
- the partially crystalline propylene polymer composition according to the invention preferably has molar masses (weight average M w ) between 50,000 and 800,000 g / mol.
- Their melt flow rates, at 230 ° C and under a weight of 2.16 kg according to ISO 1133, are in the range from 0.1 to 100 g / 10 min, preferably in the range from 0.5 to 50 g / 10 min and especially in the range of 1 to 10 g / 10 min.
- the partially crystalline propylene polymer composition according to the invention usual additives before use such as stabilizers, lubricants and mold release agents, fillers, Nucleating agents, antistatic agents, plasticizers, dyes, Pigments or flame retardants added in usual amounts.
- additives such as stabilizers, lubricants and mold release agents, fillers, Nucleating agents, antistatic agents, plasticizers, dyes, Pigments or flame retardants added in usual amounts.
- these are obtained when the powder is granulated Polymerization product incorporated into the polymer.
- Common stabilizers are antioxidants such as sterically hindered ones Phenols, processing stabilizers such as phosphites or Phosphonites, acid scavengers such as calcium or zinc stearate or dihydrotalcite, sterically hindered amines or UV stabilizers.
- the propylene polymer composition according to the invention contains one or more of the stabilizers in amounts up to 2% by weight.
- Suitable lubricants and mold release agents are, for example, fatty acids, Calcium or zinc salts of fatty acids, fatty acid amides or low molecular weight polyolefin waxes, usually in concentrations up to 2% by weight can be used.
- fillers for the propylene polymer composition e.g. Talc, chalk or glass fibers are considered, with quantities here up to 50 wt .-% can be used.
- Suitable nucleating agents are, for example, inorganic additives such as talc, silica or kaolin, salts of mono- or polycarboxylic acids such as sodium benzoate or aluminum tert-butylbenzoate, dibenzylidene sorbitol or its C 1 -C 8 -alkyl-substituted derivatives such as methyl or dimethyldibenzylidene sorbitol or salts of diesters Phosphoric acid such as sodium 2,2'-methylenebis (4,6, -di-tert-butylphenyl) phosphate.
- the content of nucleating agents in the propylene polymer composition is generally up to 5% by weight.
- Such additives are usually commercially available and are, for example in Gumbleter / Müller, Plastics Additives Handbook, 4th Edition, Hansa Publishers, Kunststoff, 1993.
- the partially crystalline propylene polymer compositions according to the invention especially for the production of foils, fibers or moldings and in particular for the production of biaxial stretched foils.
- Another object of the invention are from the invention Semi-crystalline propylene polymer compositions produced biaxially stretched films with a stretch ratio of at least 1: 3 in the longitudinal direction and at least 1: 5 in the Cross direction.
- the biaxially stretched films can be produced by melt extrusion the propylene polymer composition take place, wherein the melt discharged initially to a temperature of 100 cooled to 20 ° C to solidify them, and the solidified Film then lengthways at a temperature of 80 up to 150 ° C with a stretch ratio of at least 1: 3 and in the Transverse direction at a temperature of 120 to 170 ° C with a Stretching ratio of at least 1: 5 is stretched.
- the partially crystalline propylene polymer compositions are melted at temperatures of, for example, 220 to 300 ° C, preferably from 240 to 280 ° C, in an extruder, wherein further additives or polymers are added in the extruder can, and extrudes the melt through a flat die or an annular nozzle.
- the film obtained is then cooled to solidify.
- a flat die slot die
- take-off rollers which have a surface temperature of, for example, 10 to 100 ° C, preferably 15 to 70 ° C.
- the nozzle is usually used to cool the film tube, either air or water used with a temperature of 0 to 40 ° C.
- the film obtained is then along and across the extrusion direction stretched, leading to an orientation of the molecular chains leads.
- the order of stretching is not critical.
- the slot extrusion is usually the first Longitudinal stretching with the help of several, according to the desired Stretch ratio of roller pairs running at different speeds carried out.
- the transverse stretching then takes place by means of a corresponding clip device.
- stretching is carried out usually simultaneously in both directions by blowing in gas in the film tube.
- the longitudinal stretch ratio is usually at least 1: 3, preferably from 1: 4 to 1: 7 and especially from 1: 4.5 to 1: 5.
- the transverse stretch ratio is usually at least 1: 5, preferably from 1: 6 to 1:12 and especially from 1: 7 to 1:10.
- a heat treatment for heat setting can be applied to the biaxial stretching connect in which the film at about 0.1 to 10 s a temperature of 100 to 160 ° C is maintained. Subsequently is the film in the usual way from a winder wound up.
- one or both surfaces according to one of the known methods corona or be flame treated or if necessary with a metal such as aluminum be steamed.
- the partially crystalline according to the invention Propylene polymer composition only one or only a few Layers of a multilayer biaxially oriented Form foils.
- the from the partially crystalline propylene polymer compositions according to the invention are produced biaxially stretched films especially excellent in stiffness, barrier effect and transparency.
- Example 1 With a propylene homopolymer that is used commercially for OPP film production is used (Novolen® 1104 K from Targor GmbH), became a biaxially stretched film as in Example 1 with a thickness of approx. 20 ⁇ m.
- a melting temperature of 165.5 ° C., a melt flow rate of 3.2 g / 10 min and a proportion of 3.2% by weight soluble in xylene at room temperature were determined on the Novolen® 1104 K used. It was broken down into the fractions shown in Table 2 by TREF. The yield of the fractionation was 96.7% by weight.
- the difference Z was thus 4.0% by weight.
- Example 1 With a propylene homopolymer that is used commercially for OPP film production is used (Novolen® NQ 10134 from Targor GmbH), became a biaxially stretched film as in Example 1 with a thickness of approx. 20 ⁇ m.
- a melting temperature was reached on the Novolen® NQ 10134 used of 163.1 ° C, a melt flow rate of 3.4 g / 10 min and a portion of xylene soluble at room temperature 3.5 wt .-% determined. It was broken down into fractions by TREF. The yield of the fractionation was 97.2% by weight.
- the difference Z was thus 2.8% by weight.
- the maximum ratio M w / M n of the fractions forming component A was 2.5.
- Example 1 With a statistically constructed propylene-ethylene copolymer, which is used commercially for OPP film production (Novolen® NX 10094 from Targor GmbH), was like in Example 1 a biaxially stretched film with a thickness of about 20 ⁇ m manufactured.
- a melting temperature was set on the Novolen® NX 10094 used of 155.7 ° C, a melt flow rate of 2.9 g / 10 min, a portion soluble in xylene at room temperature of 1.7 wt .-% and an ethylene content of 1.1 wt .-% determined. It was broken down into fractions by TREF. The The yield of the fractionation was 99.7% by weight.
- the difference Z was thus 0.3% by weight.
- the maximum ratio M w / M n of the fractions forming component A was 2.8.
- Table 3 below shows the properties of the biaxially stretched films which were produced from the partially crystalline propylene polymer compositions prepared by way of example.
- example 1 Example 2 Cf. ex. A Cf. ex. B Cf. ex. C. Processing window [° C] 11 18th 12th 11 13 maximum take-off speed [m / min] 100 > 200 100 150 100 E-module in the longitudinal direction [MPa] 2600 2000 2200 2000 2200 E-module in the transverse direction [MPa] 4800 4300 4700 4500 4600 Haze [%] 2.4 1.1 2.0 1.6 2.2 H 2 O permeability [g 100 ⁇ m / (m 2 d)] 0.27 0.28 0.28 0.29 0.28 02 permeability [cm 3 100 ⁇ m / (m 2 d bar)] 410 430 430 440 430
- a comparison of the examples and comparative examples shows that the propylene polymer composition of example 1 in particular has a broader molecular weight distribution, ie an increased ratio M w / M n , in the main component A and the propylene polymer composition of example 2 has an increased proportion Minor component B has.
- Example 2 shows that not only by incorporating ethylene an inventive Composition distribution of the propylene polymer compositions can be achieved. This can also be seen from the fact that the Incorporation of 1.1% by weight of ethylene in comparative example C to reduce it the melting temperature leads to 155.7 ° C, while in example 2 despite a content of 1.5% by weight of ethylene, the melting temperature can be kept at 163.2 ° C.
- Table 3 shows that the propylene polymer composition of examples 1 in particular better mechanical Properties can be obtained without loss of workability can.
- the barrier properties are also improved (lower permeability of water vapor and oxygen).
- the Propylene polymer composition of Example 2 has one better processability and better optical properties (lower Turbidity) without sacrificing mechanical Properties of the films or the barrier properties in purchase must take.
Abstract
Description
Die vorliegende Erfindung betrifft teilkristalline Propylenpolymerisat-Zusammensetzungen, die eine besonders gute Eignung zur Herstellung von biaxial orientierten Folien aufweisen. Außerdem betrifft die Erfindung die Verwendung der teilkristallinen Propylenpolymerisat-Zusammensetzungen zur Herstellung von Folien, Fasern und Formkörpern sowie die Folien, Fasern und Formkörper aus diesen Zusammensetzungen.The present invention relates to partially crystalline propylene polymer compositions, which are particularly suitable for Have production of biaxially oriented films. Moreover The invention relates to the use of the partially crystalline propylene polymer compositions for the production of foils, Fibers and moldings and the films, fibers and moldings from these compositions.
Unter der Bezeichnung Polypropylen werden im Allgemeinen eine Vielzahl unterschiedlicher Polymerisate verstanden, die alle gemeinsam haben, daß sie zu einem wesentlichen Teil aus dem Monomer Propylen aufgebaut wurden. Die verschiedenen Polypropylene werden in der Regel durch koordinative Polymerisation an Katalysatoren aus Übergangsmetallen erhalten, die die Monomere überwiegend geordnet in eine wachsende Polymerkette einbauen.In general, under the name polypropylene Understood a variety of different polymers, all of them have in common that they are to a large extent from the monomer Propylene were built. The different polypropylenes are usually achieved through coordinative polymerization on catalysts obtained from transition metals, which predominantly the monomers built into a growing polymer chain.
Mit den üblichen Koordinationskatalysatoren erhält man bei der Polymerisation von Propylen Polymerketten, die an jedem zweiten Kohlenstoffatom eine Methylseitengruppe aufweisen. Die Polymerisation verläuft also regioselektiv. Je nach Orientierung der Monomere beim Einbau in die Kette werden verschiedene stereochemische Konfigurationen erhalten. Sind die Monomere beim Einbau jeweils gleich angeordnet, befinden sich dann in der Polymerkette alle Methylseitengruppen auf der selben Seite der Hauptkette. Man spricht von isotaktischem Polypropylen. Werden die Monomere mit jeweils alternierender räumlicher Orientierung in die Kette eingebaut, bezeichnet man das erhaltene Polypropylen als syndiotaktisch. Beide stereoregulär aufgebauten Typen sind teilkristallin und weisen somit eine Schmelztemperatur auf.With the usual coordination catalysts you get at the Polymerization of propylene polymer chains on every second Carbon atom have a methyl side group. The polymerization thus runs regioselectively. Depending on the orientation of the Monomers when incorporated into the chain become different stereochemical Get configurations. Are the monomers during installation each arranged in the same way, are then in the polymer chain all methyl side groups on the same side of the main chain. Man speaks of isotactic polypropylene. Are the monomers with alternating spatial orientation in the chain installed, the polypropylene obtained is called syndiotactic. Both types of stereoregular structure are partially crystalline and thus have a melting temperature.
Da die Koordinationskatalysatoren die Propylen-Monomere jedoch nicht absolut einheitlich einbauen, sonderen manche Monomer anders einfügen als die Mehrheit der anderen, weisen die gebildeten Polymerketten gegenüber der vorherrschenden Anordnung jeweils "Fehler" auf. Deren Anzahl kann erheblich variieren.However, since the coordination catalysts are the propylene monomers not install absolutely uniformly, some monomers insert differently than the majority of the others, show the educated Polymer chains compared to the prevailing arrangement in each case "Error" on. The number can vary considerably.
Je länger die fehlerfrei aufgebauten Sequenzen der Polymerketten sind, desto leichter kristallisieren die Ketten und desto höher sind die Kristallinität und die Schmelztemperatur des Polypropylens. The longer the error-free sequences of the polymer chains the easier the chains crystallize and the higher are the crystallinity and the melting temperature of the polypropylene.
Sind die Methylseitengruppen stereochemisch unregelmäßig angeordnet, bezeichnet man die Polypropylene als ataktisch. Diese sind vollständig amorph und weisen somit keinen Schmelzpunkt auf.If the methyl side groups are stereochemically irregularly arranged, the polypropylenes are called atactic. These are completely amorphous and therefore have no melting point.
In technischem Maßstab wird Polypropylen zur Zeit meistens mit heterogenen Katalysatoren auf Basis von Titan hergestellt, wobei ein überwiegend isotaktisches Polymerisat erzeugt wird. Diese Katalysatoren, für die sich die Bezeichnung Ziegler-Natta-Katalysatoren eingebürgert hat, weisen mehrere unterschiedliche polymerisationsaktive Zentren auf. Die Zentren unterschieden sich dabei sowohl in ihrer Stereospezifität, d.h. darin, wieviele "Fehler" die entstandenen Ketten aufweisen, als auch darin, wie hoch die mittlere Molmasse der gebildeten Ketten ist. Als überwiegende Fehler werden jeweils Stereofehler beobachtet, d.h. einzelne Propylen-Monomere wurden syndiospezifisch anstatt isospezifisch eingebaut. Das Resultat der Polymerisation mit solchen heterogenen Katalysatoren ist also eine Mischung verschiedener Polymerketten, die sich sowohl in ihrer Stereochemie als auch in ihrer Molmasse unterscheiden.On a technical scale, polypropylene is currently mostly used heterogeneous catalysts based on titanium, wherein a predominantly isotactic polymer is produced. This Catalysts, for which the name Ziegler-Natta catalysts naturalized, have several different polymerization active Centers on. The centers differed both in their stereospecificity, i.e. in how many "mistakes" the resulting chains, as well as how high the average molecular weight of the chains formed. As predominant Errors are observed in each case, i.e. individual propylene monomers were built in syndiospecific instead of isospecific. The result of the polymerization with such heterogeneous So catalysts is a mixture of different polymer chains, which differ both in their stereochemistry and in their molecular weight differentiate.
Ein wesentliches Anwendungsgebiet für Polypropylene sind Folien, insbesondere biaxial gereckten Folien, die häufig auch als BOPP-("Biaxial Orientiertes Polypropylen-")Folien bezeichnet werden.An essential area of application for polypropylenes is foils, especially biaxially stretched films, which are often called BOPP - ("Biaxially Oriented Polypropylene -") films.
Eine generelles Ziel für fast alle Entwicklungen auf dem Gebiet der Polypropylene ist es, die löslichen Anteile der eingesetzten Polymerisate zu verringern. Möglich ist dies häufig durch die Verwendung optimierter konventioneller Ziegler-Natta-Katalysatoren. Dadurch werden zum einen die organoleptischen Eigenschaften verbessert, was vorteilhaft für Anwendungen im medizinischen und Nahrungsmittelsektor ist, und zum anderen wirkt sich dies positiv auf die mechanischen Eigenschaften, insbesondere die Steifigkeit, aus. Für die Herstellung von biaxial gereckten Polypropylen-Folien lassen sich solche Polypropylene mit abgesenkten löslichen Anteilen allerdings nicht einsetzen, da sie sich nicht bzw. nur schlecht zu den Folien verarbeiten lassen. Es wurden deshalb eine Reihe von Anstrengungen unternommen, durch Variationen in der Zusammensetzung für die Herstellung von biaxial gereckten Polypropylen-Folien geeignete Polypropylene zu finden.A general goal for almost all developments in the field The polypropylene is used to dissolve the soluble parts To reduce polymers. This is often possible through the Use of optimized conventional Ziegler-Natta catalysts. On the one hand, this gives the organoleptic properties improves what is advantageous for applications in medical and Food sector, and on the other hand this has a positive effect on the mechanical properties, especially the rigidity, out. For the production of biaxially stretched polypropylene films such polypropylenes can be used with lowered soluble However, do not use shares as they do not or can only be processed poorly to the foils. It was because of that a number of efforts have been made through variations in the composition for the production of biaxially stretched Polypropylene films to find suitable polypropylenes.
In der EP-A 339 804 wird eine Mischung aus einem Homopolypropylen und einem statistischen Propylencopolymerisat beschrieben, wobei das Comonomer im oberen Bereich der Molekulargewichtsverteilung der Mischung eingebaut ist. Solche Mischungen weisen gute optische und mechanische Eigenschaften auf, sind aber in der Verarbeitbarkeit eingeschränkt.EP-A 339 804 describes a mixture of a homopolypropylene and a statistical propylene copolymer, wherein the comonomer in the upper range of the molecular weight distribution the mixture is built in. Such mixtures have good optical properties and mechanical properties, but are processable limited.
Die EP-A 115 940 offenbart zur Herstellung von biaxial gereckten Folien geeignete Propylen-Ethylen-Copolymerisate mit 0,1 bis 2,0 mol% Ethylen und einer hohen Isotaktizität. Diese Polymerisate besitzen eine gute Dehnbarkeit, Steifigkeit, Transparenz, Schlagzähigkeit und Wärmeschrumpfbeständigkeit. Allerdings genügen sie in ihren mechanischen, rheologischen und optischen Eigenschaften häufig noch nicht den Ansprüchen der Hersteller von BOPP-Folien.EP-A 115 940 discloses for the production of biaxially stretched Suitable propylene-ethylene copolymers with 0.1 to 2.0 mol% ethylene and high isotacticity. These polymers have good elasticity, rigidity, transparency, Impact resistance and heat shrink resistance. However, it is enough they in their mechanical, rheological and optical properties often not yet meet the requirements of the manufacturers of BOPP films.
Die EP-A 657 476 beschreibt ein α-Olefinpolymerisat, erhalten durch Polymerisation eines α-Olefins mit 3 oder mehr Kohlenstoffatomen, dessen Zusammensetzung über die Gewichtsanteile an bei 20°C in Xylol löslichen und an bei 105°C in Xylol unlöslichen Anteilen definiert ist.EP-A 657 476 describes an α-olefin polymer obtained by polymerizing an α-olefin with 3 or more carbon atoms, whose composition is based on the proportions by weight 20 ° C soluble in xylene and insoluble at 105 ° C in xylene Shares is defined.
In der JP-A 10 053 675 wird eine Polypropylenzusammensetzung beschrieben, bestehend aus einem hochmolekularen kristallinen Polypropylen mit einem löslichen Anteil von weniger als 5% und einer niedermolekularen Polyolefinmasse mit einem löslichen Anteil von mehr als 30%.JP-A 10 053 675 describes a polypropylene composition described, consisting of a high molecular weight crystalline Polypropylene with a soluble content of less than 5% and a low molecular weight polyolefin mass with a soluble Share of more than 30%.
Die aus dem Stand der Technik bekannten Propylenpolymerisat-Zusammensetzungen ermöglichen zwar die Herstellung von biaxial orientierten Polypropylen-Folien, sie weisen jedoch nicht gleichzeitig eine optimale Verarbeitbarkeit und sehr gute mechanische Eigenschaften der Folien auf. Dies bedeutet, daß es bisher nicht gelungen ist, den gegenläufigen Zusammenhang zwischen Verarbeitbarkeit und mechanischen Eigenschaften der Folien zu entkoppeln. Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, Propylenpolymerisat-Zusammensetzungen zu entwickeln, die gleichzeitig eine hervorragende Verarbeitbarkeit zu biaxial gereckten Folien aufweisen und aus denen sich Folien mit sehr guten mechanischen und optischen Eigenschaften herstellen lassen. Weiterhin sollten diese mit einem möglichst wenig aufwendigen Verfahren zugänglich sein und die Folien sollten eine gute Barrierewirkung, beispielsweise gegen Sauerstoff und Wasserdampf, besitzen.The propylene polymer compositions known from the prior art enable the production of biaxial oriented polypropylene films, however, they do not show at the same time optimal processability and very good mechanical Properties of the films. This means that it has not so far managed to reverse the relationship between processability and decouple mechanical properties of the foils. The present invention was therefore based on the object of propylene polymer compositions to develop that at the same time excellent processability to biaxially stretched films have and from which films with very good mechanical and have optical properties manufactured. Furthermore, should accessible with the least possible complex process and the films should have a good barrier effect, for example against oxygen and water vapor.
Demgemäß wurden teilkristalline Propylenpolymerisat-Zusammensetzung,
hergestellt durch Polymerisation von Propylen, Ethylen und/
oder C4-C18-Alk-1-enen, wobei mindestens 50 mol-% der enthaltenen
Monomereinheiten durch Polymerisation von Propylen entstanden
sind, gefunden, die eine guter Eignung zur Herstellung von
biaxial orientierten Folien aufweisen,
wobei deren Schmelztemperatur TM im Bereich von 65°C bis 170°C
liegt und die Schmelztemperatur TM durch Differential Scanning
Calorimetry (DSC) nach ISO-Norm 3146 durch Aufheizen mit einer
Heizgeschwindigkeit von 20°C/min einer vorher aufgeschmolzenen
Probe bestimmt und in °C gemessen wird und das Maximum der erhaltenen
Kurve darstellt,
und wobei sich die teilkristalline Propylenpolymerisat-Zusammensetzung
in
the melting temperature T M is in the range from 65 ° C to 170 ° C and the melting temperature T M is determined by differential scanning calorimetry (DSC) according to ISO standard 3146 by heating at a heating rate of 20 ° C / min of a previously melted sample and is measured in ° C and represents the maximum of the curve obtained,
and wherein the partially crystalline propylene polymer composition in
wobei man zur Bestimmung der Anteile der Komponenten A, B und C eine TREF (Temperature Rising Elution Fractionation) durchführt, bei der man die Polymerisate zunächst in siedendem Xylol löst, anschließend die Lösung mit einer Kühlrate von 10°C/h auf 25°C abkühlt und dann mit steigender Temperatur zunächst den bei der Temperatur (TM/2)+7,5°C in Xylol löslichen Anteil der Propylenpolymerisat-Zusammensetzung löst und vom verbleibenden Feststoff abtrennt und anschließend mit steigender Temperatur bei allen höheren Temperaturen 70°C, 75°C, 80°C, 85°C, 90°C, 94°C, 98°C, 102°C, 107°C, 112°C, 117°C, 122°C und 125°C die im Temperaturintervall zwischen dieser Elutionstemperatur und der vorhergehenden Elutionstemperatur löslichen Fraktionen eluiert und diejenigen Fraktionen bei der weiteren Auswertung berücksichtigt, deren Masseanteil an der eingewogenen Propylenpolymerisat-Zusammensetzung mindestens 1 Gew.-% beträgt, und von allen zu berücksichtigenden Fraktionen die Molmassenverteilung durch Gelpermeationschromatographie (GPC) bei 145°C in 1,2,4-Trichlorbenzol mißt,where a TREF (Temperature Rising Elution Fractionation) is carried out to determine the proportions of components A, B and C, in which the polymers are first dissolved in boiling xylene, then the solution at a cooling rate of 10 ° C / h to 25 ° C cools and then, with increasing temperature, first dissolves the portion of the propylene polymer composition which is soluble in xylene at the temperature (T M / 2) + 7.5 ° C. and separates it from the remaining solid and then 70 ° C. with increasing temperature at all higher temperatures, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 94 ° C, 98 ° C, 102 ° C, 107 ° C, 112 ° C, 117 ° C, 122 ° C and 125 ° C in the temperature interval fractions soluble between this elution temperature and the previous elution temperature and those fractions taken into account in the further evaluation whose mass fraction of the weighed propylene polymer composition is at least 1% by weight and of all fractions to be taken into account n measures the molar mass distribution by gel permeation chromatography (GPC) at 145 ° C. in 1,2,4-trichlorobenzene,
und die Hauptkomponente A von allen Fraktionen gebildet wird, die
bei einer Temperatur oberhalb von (TM/2)+7,5°C eluiert werden und
eine mittlere Molmasse MN (Zahlenmittel) ≥ 120 000 g/mol aufweisen,
Außerdem wurden teilkristalline Propylenpolymerisat-Zusammensetzung
mit guter Eignung zur Herstellung von biaxial orientierten
Folien, hergestellt durch Polymerisation von Propylen, Ethylen
und/oder C4-C18-Alk-1-enen, wobei mindestens 50 mol-% der enthaltenen
Monomereinheiten durch Polymerisation von Propylen entstanden
sind, mit einer Schmelztemperatur TM im Bereich von 65°C bis
170°C gefunden,
wobei sich die teilkristalline Propylenpolymerisat-Zusammensetzung
in
the partially crystalline propylene polymer composition in
Weiterhin wurde auch die Verwendung der teilkristallinen Propylenpolymerisat-Zusammensetzung zur Herstellung von Folien, Fasern und Formkörpern sowie die Folien, Fasern und Formkörper aus dieser Zusammensetzung gefunden.Furthermore, the use of the partially crystalline propylene polymer composition for the production of foils, fibers and moldings, and the films, fibers and moldings made from them Composition found.
Die erfindungsgemäßen teilkristallinen Propylenpolymerisat-Zusammensetzungen werden durch Polymerisation von Propylen, Ethylen und/oder C4-C18-Alk-1-enen hergestellt. Unter der Bezeichnung C4-C18-Alk-1-ene sollen lineare oder verzweigte Alk-1-ene verstanden werden, die von vier bis achtzehn Kohlenstoffatome aufweisen. Bevorzugt sind lineare Alk-1-ene. Insbesondere sind Ethylen, But-1-en, Pent-1-en, Hex-1-en, Hept-1-en oder Oct-1-en oder Gemische aus diesen Comonomeren zu nennen, wobei bevorzugt Ethylen oder But-1-en verwendet wird. Die Propylenpolymerisat-Zusammensetzungen enthalten mindestens 50 mol-% an Monomereinheiten, die durch Polymerisation von Propylen entstanden sind. Bevorzugt ist der Gehalt an von Propylen abgeleiteten Monomereinheiten mindestens 70 mol-% und insbesondere mindestens 85 mol-%. In einer weiteren bevorzugten Ausführungsform wird bei der Herstellung der erfindungsgemäßen Propylenpolymerisat-Zusammensetzungen als einziges Monomer Propylen eingesetzt, d.h. es handelt sich um ein Propylenhomopolymerisat. Falls ein oder mehrere Comonomere verwendet wurden, kann es sein, daß die ganze Propylenpolymerisat-Zusammensetzung eine im wesentlichen gleiche Comonomerverteilung im Sinne von statistischen Copolymerisaten besitzt. Es kann aber auch sein, daß es sich wie bei den sogenannten Propylen-Impact-copolymerisaten um eine Mischung verschiedener Komponenten handelt, die unterschiedliche Comonomergehalte aufweisen.The partially crystalline propylene polymer compositions according to the invention are prepared by polymerizing propylene, ethylene and / or C 4 -C 18 -alk-1-enes. The term C 4 -C 18 alk-1-enes is understood to mean linear or branched alk-1-enes which have from four to eighteen carbon atoms. Linear alk-1-enes are preferred. Ethylene, but-1-ene, pent-1-ene, hex-1-ene, hept-1-ene or oct-1-ene or mixtures of these comonomers may be mentioned, preference being given to ethylene or but-1-ene is used. The propylene polymer compositions contain at least 50 mol% of monomer units which are formed by polymerizing propylene. The content of monomer units derived from propylene is preferably at least 70 mol% and in particular at least 85 mol%. In a further preferred embodiment, propylene is used as the only monomer in the preparation of the propylene polymer compositions according to the invention, ie it is a propylene homopolymer. If one or more comonomers were used, it may be that the entire propylene polymer composition has an essentially identical comonomer distribution in the sense of statistical copolymers. However, it may also be the case that, like the so-called propylene impact copolymers, it is a mixture of different components which have different comonomer contents.
Die erfindungsgemäßen teilkristallinen Propylenpolymerisat-Zusammensetzungen weisen eine Schmelztemperatur TM auf, die im Bereich von 65°C bis 170°C und bevorzugt im Bereich von 135°C bis 165°C liegt.The partially crystalline propylene polymer compositions according to the invention have a melting temperature T M which is in the range from 65 ° C. to 170 ° C. and preferably in the range from 135 ° C. to 165 ° C.
Unter der Schmelztemperatur TM ist hierbei die Temperatur zu verstehen, bei der die durch Differential Scanning Calorimetry (DSC) nach ISO-Norm 3146 durch Aufheizen mit einer Heizgeschwindigkeit von 20°C/min einer vorher aufgeschmolzenen Probe erhaltenen Kurve der Enthalpie gegen die Temperatur das Maximum aufweist. Die DSC-Messung wird dabei üblicherweise so durchgeführt, daß man zunächst die Probe mit einer Aufheizrate von 20°C/min bis etwa 40°C über die Schmelztemperatur erwärmt, die Probe dann mit einer Kühlrate von 20°C/min dynamisch kristallisieren läßt und bei einem zweiten Aufheizen mit einer Aufheizrate von 20°C/min die Schmelztemperatur TM bestimmt.The melting temperature T M is to be understood here as the temperature at which the enthalpy versus temperature curve obtained by differential scanning calorimetry (DSC) in accordance with ISO standard 3146 by heating at a heating rate of 20 ° C./min of a previously melted sample Maximum. The DSC measurement is usually carried out by first heating the sample at a heating rate of 20 ° C./min to about 40 ° C. above the melting temperature, then dynamically crystallizing the sample at a cooling rate of 20 ° C./min and with a second heating with a heating rate of 20 ° C / min the melting temperature T M is determined.
Zur Bestimmung der Anteile der Komponenten A, B und C an der teilkristallinen Propylenpolymerisat-Zusammensetzungen führt man erfindungsgemäß eine Fraktionierung mittels TREF (Temperature Rising Elution Fractionation) durch und mißt dann die Molmassenverteilung aller Fraktionen durch Gelpermeationschromatographie (GPC).To determine the proportions of components A, B and C in the Semi-crystalline propylene polymer compositions are carried out fractionation according to the invention by means of TREF (temperature Rising Elution Fractionation) and then measures the molecular weight distribution all fractions by gel permeation chromatography (GPC).
GPC und TREF sind Methoden, mittels denen Polymerproben anhand unterschiedlicher physikalischer Eigenschaften aufgetrennt werden können. Während die GPC Polymerketten aufgrund ihrer Größe fraktioniert, erfolgt die Trennung bei der TREF nach der Kristallisierbarkeit der Polymermoleküle. Das Prinzip der "Temperature rising elution fractionation" wurde beispielsweise ausführlich von L. Wild, Advances in Polymer Sciences 98, 1 - 47 (1990) beschrieben. Hierbei wird eine Polymerprobe bei erhöhter Temperatur in einem Lösungsmittel gelöst, wobei die Konzentration der Lösung kleiner als 2 Gew.-% sein sollte. Die Polymerlösung wird nun sehr langsam (ca. 0,1°C/min) abgekühlt. Zuerst fallen dann die Polymermoleküle aus, die sehr gut kristallisieren und später Moleküle mit schlechteren Kristallisationseigenschaften. In dem Lösungsmittel entstehen somit Polymerpartikel, bei denen die Kristallisierbarkeit der Moleküle, aus denen sie bestehen, von innen nach außen abnimmt. Nach dem Abkühlen folgt die eigentliche Fraktionierung durch Aufheizen der Polymersuspension. Dabei werden zuerst bei relativ niedriger Temperatur die schlecht kristallisierenden Moleküle, die sich am äußeren Rand der Polymerpartikel befinden, aufgelöst und mit dem Lösungsmittel, in dem sie gelöst sind, abgetrennt. Bei höherer Temperatur folgen die besser kristallisierenden Polymerketten.GPC and TREF are methods that are used to measure polymer samples different physical properties can be separated can. While the GPC fractionates polymer chains based on their size, the TREF separates according to the crystallizability of the polymer molecules. The principle of "Temperature rising elution fractionation "has been detailed, for example by L. Wild, Advances in Polymer Sciences 98, 1-47 (1990) described. This is a polymer sample at an elevated temperature dissolved in a solvent, the concentration of Solution should be less than 2 wt .-%. The polymer solution will now cooled very slowly (approx. 0.1 ° C / min). First they fall Polymer molecules that crystallize very well and later molecules with poorer crystallization properties. In the solvent This creates polymer particles in which the crystallizability of the molecules that make it up, from the inside decreases towards the outside. After cooling, the actual fractionation follows by heating the polymer suspension. In doing so the poorly crystallizing ones first at a relatively low temperature Molecules that are on the outer edge of the polymer particles are dissolved and with the solvent in which they are dissolved are separated. At higher temperatures, the more crystallizing ones follow Polymer chains.
Als besonders geeignet zur Durchführung einer TREF hat sich die in Fig. 1 schematisch dargestellte Apparatur erwiesen. Diese besteht aus einem temperierbaren Vorratsgefäß (1), einem temperierbaren Elutionsgefäß (2), zwei Thermostaten (3) (beispielsweise Typ HC5 der Fa. Julabo), zwei Temperaturfühlern (4) und einem leistungsfähigen Mischer (5), mit dem die Polymersuspension durchmischt wird. Im unteren Teil des Elutionsgefäßes befindet sich durch ein Drahtnetz abgetrennte Glaswolle (6), die verhindert, daß beim Ablassen von Polymerlösungen ungelöste Polymerpartikel ausgetragen werden.The has proven to be particularly suitable for carrying out a TREF 1 apparatus shown schematically. This consists of a temperature-controlled storage vessel (1), a temperature-controlled one Elution vessel (2), two thermostats (3) (for example Type HC5 from Julabo), two temperature sensors (4) and a powerful mixer (5) with which the polymer suspension is mixed. Located in the lower part of the elution tube glass wool (6) separated by a wire mesh, which prevents that undissolved polymer particles when draining polymer solutions be carried out.
Um die teilkristallinen Propylenpolymerisat-Zusammensetzungen erfindungsgemäß zu charakterisieren, wird zunächst das Polymerisat in Xylol gelöst. Prinzipiell können hierbei alle Xylol-Isomere, Isomerenmischungen oder Isomerenmischungen mit Anteilen von Ethylbenzol verwendet werden, wobei aus wirtschaftlichen Erwägungen Isomermischungen bevorzugt sind. Allerdings ist es vorteilhaft weder reines p-Xylol noch Isomerenmischungen mit einem Anteil an p-Xylol von mehr als etwa 50 Gew.-% einzusetzen, da p-Xylol einen Festpunkt bei etwa 20°C besitzt.To the semi-crystalline propylene polymer compositions To characterize according to the invention is first the polymer dissolved in xylene. In principle, all xylene isomers, Isomer mixtures or isomer mixtures with proportions of Ethylbenzene may be used for economic reasons Isomer mixtures are preferred. However, it is beneficial neither pure p-xylene nor isomer mixtures with one Use of p-xylene of more than about 50 wt .-%, because p-xylene has a fixed point at about 20 ° C.
Die Polymerprobe wird zum Lösen beispielsweise zusammen mit dem Lösungsmittel in ein Glasgefäß mit Magnetrührstab und aufgesetztem Rückflußkühler gegeben und das Glasgefäß danach in einem Temperierbad unter Rühren bis zum vollständigen Auflösen des Polymers erhitzt. Die Polymerlösung wird anschließend, z.B. durch Absenken des Glasgefäßes in das vorgeheizte Ölbad eines Thermostaten, mit einer Abkühlrate von 10°C/h bis auf Raumtemperatur gekühlt. Das definierte Abkühlen kann man durch die entsprechende Programmierung eines mit dem Thermostaten verbundenen Programmgebers erreichen. Üblicherweise werden für jede TREF-Analyse 5 g Propylenpolymerisat in 400 ml Xylol gelöst. The polymer sample is used for dissolution together with the Solvent in a glass jar with magnetic stir bar and attached Given a reflux condenser and then the glass vessel in one Tempering bath with stirring until the Polymers heated. The polymer solution is then e.g. by Lowering the glass vessel into the preheated oil bath of a thermostat, with a cooling rate of 10 ° C / h to room temperature chilled. The defined cooling can be done by the corresponding one Programming a programmer connected to the thermostat to reach. Usually 5 g for each TREF analysis Propylene polymer dissolved in 400 ml xylene.
Die durch das definierte Auskristallisieren entstandene Polymersuspension wird in das Elutionsgefäßes (2) der in Fig. 1 gezeigten Apparatur überführt, die Temperatur auf (TM/2)+7,5°C erwärmt und die Polymerkristalle bei dieser Temperatur unter heftiger Durchmischung 15 Minuten extrahiert. Die Polymerlösung wird dann abgelassen, während die Kristalle im Extraktor zurückbleiben. Das gelöste Polymer wird vorzugsweise in kaltem Aceton (Temperatur < 0°C) ausgefällt, abfiltriert und 4 bis 5 Stunden bei 100°C im Vakuum getrocknet.The polymer suspension resulting from the defined crystallization is transferred into the elution vessel (2) of the apparatus shown in FIG. 1, the temperature is heated to (T M / 2) + 7.5 ° C. and the polymer crystals at this temperature with vigorous mixing for 15 minutes extracted. The polymer solution is then drained off while the crystals remain in the extractor. The dissolved polymer is preferably precipitated in cold acetone (temperature <0 ° C), filtered off and dried in vacuo at 100 ° C for 4 to 5 hours.
Anschließend werden 400 ml Xylol, das auf die nächst höhere der Temperaturen 70°C, 75°C, 80°C, 85°C, 90°C, 94°C, 98°C, 102°C, 107°C, 112°C, 117°C, 122°C und 125°C temperiert ist, den Polymerkristallen im Elutionsgefäß (2) zugegeben. Es wird wiederum 15 Minuten bei dieser nächst höheren Temperatur durchmischt. Hierbei gehen die im Temperaturintervall zwischen dieser Elutionstemperatur und der vorhergehenden Elutionstemperatur löslichen Anteile der teilkristallinen Propylenpolymerisat-Zusammensetzung in Lösung. Die entstandene Lösung wird dann abgelassen, während die Kristalle im Extraktor zurückbleiben.Then 400 ml of xylene, the next higher the Temperatures 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 94 ° C, 98 ° C, 102 ° C, 107 ° C, 112 ° C, 117 ° C, 122 ° C and 125 ° C, the polymer crystals added in the elution vessel (2). It will turn Mix for 15 minutes at this next higher temperature. Here, the temperature range between this elution temperature and the previous elution temperature Proportions of the partially crystalline propylene polymer composition in solution. The resulting solution is then drained off while the crystals remain in the extractor.
Dieses Prozedere wird so lange wiederholt, bis alle Polymerkristalle in Lösung gegangen sind. Bei allen bisher untersuchen Polypropylenen war dies spätestens bei der Temperatur 125°C erreicht.This procedure is repeated until all the polymer crystals have gone into solution. Examine all of them so far This was polypropylene at 125 ° C at the latest reached.
Die gelösten Polymere der einzelnen Fraktionen werden vorzugsweise in kaltem Aceton (Temperatur < 0°C) ausgefällt, abfiltriert und 4 bis 5 Stunden bei 100°C im Vakuum getrocknet.The dissolved polymers of the individual fractions are preferred precipitated in cold acetone (temperature <0 ° C), filtered off and Dried in vacuo for 4 to 5 hours at 100 ° C.
Da bei der Fraktionierung einer Polymerisat-Zusammensetzung immer gewisse, wenn auch geringfügige Verluste auftreten, ist in der Regel die Summe der Mengen der Fraktionen niedriger als als die eingewogene Menge an Polymerisat. Solange mindestens 96 Gew.-% der eingewogene Menge des Propylenpolymerisat-Zusammensetzung in den Fraktionen wiedergefunden wird, ist dies unbeachtlich. Sollte der Verlust jedoch höher sein, muß die Fraktionierung wiederholt werden.Because when fractionating a polymer composition always certain, albeit minor, losses occur in the Usually the sum of the amounts of the fractions is lower than that weighed amount of polymer. As long as at least 96% by weight the weighed amount of the propylene polymer composition in the factions are recovered, this is irrelevant. Should however, if the loss is higher, the fractionation must be repeated become.
Weiterhin ist es nicht möglich, mit extrem kleinen Probemengen zuverlässig die Molmassenverteilung zu bestimmen. Um Fehler zu minimieren, ist die weitere Auswertung deshalb so durchzuführen, daß nur solche Fraktionen bei der Berechnung der Komponenten A, B und C berücksichtigt werden, deren Massenanteil an der eingewogenen Polymerprobe mindestens 1 Gew.-% beträgt. Von diesen Fraktionen wird die Molmassenverteilung durch Gelpermeationschromatographie (GPC) in 1,2,4-Trichlorbenzol bei 145°C bestimmt, wobei die Kalibrierung der GPC mittels Polypropylenstandards mit Molmassen von 100 bis 107 g/mol erfolgt.Furthermore, it is not possible to reliably determine the molecular weight distribution using extremely small sample quantities. In order to minimize errors, the further evaluation should therefore be carried out in such a way that only those fractions are taken into account in the calculation of components A, B and C whose mass fraction in the weighed polymer sample is at least 1% by weight. The molecular weight distribution of these fractions is determined by gel permeation chromatography (GPC) in 1,2,4-trichlorobenzene at 145 ° C., the GPC being calibrated using polypropylene standards with molecular weights of 100 to 107 g / mol.
Entsprechend der Temperatur, bei der die jeweilige Fraktion eluiert wurde, d.h. der Temperatur bei der die Polymerketten entsprechend der des Temperaturfolge 70°C, 75°C, 80°C, 85°C, 90°C, 94°C, 98°C, 102°C, 107°C, 112°C, 117°C, 122°C in Lösung gegangen sind, und der mittleren Molmasse Mn (Zahlenmittel) der jeweilige Fraktion lassen sich die Fraktionen nun den einzelnen Komponenten A, B und C zuordnen.According to the temperature at which the respective fraction was eluted, ie the temperature at which the polymer chains corresponded to that of the temperature sequence 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 94 ° C, 98 ° C , 102 ° C, 107 ° C, 112 ° C, 117 ° C, 122 ° C have gone into solution, and the average molar mass M n (number average) of the respective fraction, the fractions can now be the individual components A, B and C. assign.
Die Hauptkomponente A wird von allen zu berücksichtigenden Fraktionen
gebildet, die bei einer Temperatur oberhalb von
(TM/2)+7,5°C eluiert werden und eine mittlere Molmasse
Mn (Zahlenmittel) ≥ 120 000 g/mol aufweisen.The main component A is formed by all fractions to be taken into account, which are eluted at a temperature above (T M / 2) + 7.5 ° C and an average molecular weight
M n (number average) ≥ 120,000 g / mol.
Die Nebenkomponente B wird von der Fraktion gebildet, die bei der Temperatur (TM/2)+7,5°C eluiert wird. Wenn der Anteil der bei der Temperatur (TM/2)+7,5°C eluierten Fraktion an der gesamten Propylenpolymerisat-Zusammensetzung kleiner 1 Gew.-% ist, ist somit der Anteil der Nebenkomponente B entsprechend der oben gegebenen Definition der zu berücksichtigenden Fraktionen gleich 0 Gew.-%.The secondary component B is formed by the fraction which is eluted at the temperature (T M / 2) + 7.5 ° C. If the proportion of the fraction eluted at the temperature (T M / 2) + 7.5 ° C. in the total propylene polymer composition is less than 1% by weight, the proportion of secondary component B according to the definition given above is the one to be taken into account Fractions equal to 0% by weight.
Die Nebenkomponente C wird von allen zu berücksichtigenden Fraktionen
gebildet wird, die bei einer Temperatur oberhalb von
(TM/2)+7,5°C eluiert werden und eine mittlere Molmasse
Mn (Zahlenmittel) < 120 000 g/mol aufweisen.The secondary component C is formed by all fractions to be taken into account, which are eluted at a temperature above (T M / 2) + 7.5 ° C and an average molecular weight
Mn (number average) <120,000 g / mol.
Bedingt durch die Verluste bei der TREF und dadurch, daß Fraktionen,
die einem Anteil an der Propylenpolymerisat-Zusammensetzung
von weniger als 1 Gew.-% haben, nicht weiter berücksichtigt werden,
ist die Summe der experimentell erhaltene Mengen an Komponenten
A, B und C geringer als die bei der Fraktionierung eingewogene
Menge an Polymerisat, auf die bezogen wird. Da die Anteile
der Komponenten A, B und C üblicherweise in Gew.-% angeben werden,
ergibt sich somit für die Summe der Anteile der Komponenten
A, B und C eine Differenz zu 100 Gew.-%, die man als Z bezeichnen
und entsprechend der Formel
Zur Deutung der guten Eigenschaften der erfindungsgemäßen Propylenpolymerisat-Zusammensetzungen kann man annehmen, daß insbesondere ein hoher Gehalt an Hauptkomponente A eine hohe Steifigkeit der Folien bewirkt. Der Gehalt an Nebenkomponente B beeinflußt die Geschwindigkeit der Verarbeitung und der Gehalt an Nebenkomponente C ist für ein breites Temperaturfenster verantwortlich.To interpret the good properties of the propylene polymer compositions according to the invention one can assume that in particular a high content of main component A high rigidity of the foils. The content of minor component B affects the speed of processing and the content of secondary components C is responsible for a wide temperature window.
Eine weitere Größe zur Charakterisierung der erfindungsgemäßen Propylenpolymerisat-Zusammensetzungen ist der bei Raumtemperatur in Xylol lösliche Anteil XL, unter dem der nach einem Verfahren analog der ISO-Norm 1873-1:1991 bestimmte Anteile zu verstehen ist. Hierbei werden 5 g Polypropylen in 500 ml destilliertes Xylol, das zuvor auf 100°C erhitzt wurde, gegeben. Anschließend erhitzt man die Mischung auf den Siedepunkt des Xylols und hält 60 min bei dieser Temperatur. Daraufhin wird innerhalb von 20 min mit einem Kältebad auf 5°C abgekühlt und dann wieder auf 20°C erwärmt. Diese Temperatur wird für 30 min gehalten. Das ausgefallene Polymerisat filtriert man ab. Von dem Filtrat werden exakt 100 ml abgefüllt und das Lösungsmittel am Rotationsverdampfer entfernt. Der verbleibende Rückstand wird für ca. 2 h bei 80°C/250 mbar bis zur Gewichtskonstanz getrocknet und nach dem Erkalten ausgewogen.Another parameter for the characterization of the invention Propylene polymer compositions is that at room temperature in xylene soluble portion XL, below that by a process to understand certain proportions analogous to ISO standard 1873-1: 1991 is. 5 g of polypropylene are distilled in 500 ml Xylene, which was previously heated to 100 ° C, added. Subsequently the mixture is heated to the boiling point of the xylene and held 60 min at this temperature. Then within 20 min cooled to 5 ° C with a cold bath and then back to 20 ° C warmed up. This temperature is held for 30 minutes. The fancy Polymer is filtered off. The filtrate will be exact 100 ml filled and the solvent on a rotary evaporator away. The remaining residue is left for about 2 h 80 ° C / 250 mbar dried to constant weight and after Cold balanced.
Der xylollösliche Anteil ergibt sich aus
- XL =
- xylollöslicher Anteil in %,
- g =
- gefundene Menge in g,
- G =
- Produkteinwaage in g,
- V =
- Volumen der eingesetzten Filtratmenge in ml.
- X L =
- xylene-soluble fraction in%,
- g =
- found quantity in g,
- G =
- Product weight in g,
- V =
- Volume of the amount of filtrate used in ml.
Gemäß einer der Ausführungsformen der vorliegenden Erfindung lassen
sich die erfindungsgemäßen teilkristallinen Propylenpolymerisat-Zusammensetzungen
in
Die teilkristallinen Propylenpolymerisat-Zusammensetzungen gemäß dieser Ausführungsform weisen also eine breite Molmassenverteilung der hochisotaktischen Anteile aus. Sie zeichnen sich dadurch aus, daß gegenüber herkömmlichen, zur Herstellung von BOPP-Folien eingesetzten Polypropylenen beispielsweise verbesserte mechanische Eigenschaften der Folien und verbesserte Barriereeigenschaften erreicht werden, ohne daß es Nachteile in der Verarbeitbarkeit gibt.The partially crystalline propylene polymer compositions according to This embodiment therefore has a broad molar mass distribution of the highly isotactic components. You are characterized by it from that compared to conventional, for the production of BOPP films Polypropylenes used, for example, improved mechanical Properties of the films and improved barrier properties can be achieved without there being disadvantages in processability gives.
Die teilkristallinen Propylenpolymerisat-Zusammensetzungen gemäß
einer weiteren der Ausführungsformen der vorliegenden Erfindung
lassen sich in
Die teilkristallinen Propylenpolymerisat-Zusammensetzungen gemäß dieser Ausführungsform haben einen relativ hohen Gehalt an niedertaktischen Anteilen, die bei einer Temperatur (TM/2)+7,5°C jedoch nicht bei Raumtemperatur in Xylol löslich sind und niedrige bei Raumtemperatur in Xylol lösliche Anteile. Sie zeichnen sich dadurch aus, daß sie gegenüber herkömmlichen, zur Herstellung von BOPP-Folien eingesetzten Polypropylenen eine verbesserte Verarbeitbarkeit aufweisen, was sich in einem verbreiterten Temperaturverarbeitungsfenster und einem verbreiterten Geschwindigkeitsverarbeitungsfenster widerspiegelt, und die optischen Eigenschaften der Folien verbessert sind, ohne daß Nachteile in den mechanischen Eigenschaften der Folien auftreten.The semicrystalline propylene polymer compositions according to this embodiment have a relatively high content of low-tactical fractions which, however, are not soluble in xylene at a temperature (T M / 2) + 7.5 ° C. and low fractions soluble in xylene at room temperature. They are characterized in that they have improved processability compared to conventional polypropylenes used for the production of BOPP films, which is reflected in a widened temperature processing window and a widened speed processing window, and the optical properties of the films are improved without disadvantages in the mechanical properties of the films occur.
Wesentlich für die Eigenschaften der erfindungsgemäßen Propylenpolymerisat-Zusammensetzungen ist deren Anteil an den Komponenten A, B und C. Das Verfahren, nach dem die jeweiligen Mischungen unterschiedlicher Polymerketten hergestellt wurden, ist an sich nicht kritisch.Essential for the properties of the propylene polymer compositions according to the invention is their share of the components A, B and C. The process by which the respective mixtures are different Polymer chains were made in itself not critical.
Beispielsweise ist es möglich, zwei oder mehrere Ausgangspolymerisate getrennt zu polymerisieren und diese dann mit geeigneten Mischeinrichtungen wie Schnecken- oder Scheibenextrudern, Knetern oder Walzwerken zu mischen.For example, it is possible to use two or more starting polymers to polymerize separately and then with suitable Mixing devices such as screw or disk extruders, kneaders or to mix rolling mills.
Vorzugsweise werden die Propylenpolymerisat-Zusammensetzungen jedoch nicht getrennt polymerisiert. Eine Möglichkeit besteht dann darin, daß eine Mischung von zwei oder mehreren verschiedenen Katalysatoren eingesetzt wird, die unter den eingestellten Polymerisationsbedingungen unterschiedliche Polypropylene liefern, oder es wird ein Katalysator verwendet der von sich aus so unterschiedliche aktive Zentren besitzt, daß er als solcher entsprechende Mischungen von Polymerketten liefert. Eine andere Möglichkeit ist, unter so unterschiedlichen Bedingungen in verschiedenen Reaktoren, beispielsweise einer Reaktorkaskade, zu polymerisieren, daß letztendlich die gewünschte Zusammensetzung resultiert.The propylene polymer compositions are preferred but not polymerized separately. There is a possibility then in that a mixture of two or more different ones Catalysts are used that are set under the Polymerization conditions different polypropylenes deliver, or a catalyst is used by itself has such different active centers that he as such provides appropriate mixtures of polymer chains. Another Possibility is in so different conditions in different Reactors, for example a reactor cascade that ultimately polymerize to the desired composition results.
Die Herstellung der Bestandteile der erfindungsgemäßen Propylenpolymerisat-Zusammensetzung oder der gesamten Propylenpolymerisat-Zusammensetzung kann in bekannter Weise in Masse, in Suspension oder in der Gasphase in den üblichen, für die Polymerisation von Propylen verwendeten Reaktoren entweder absatzweise oder bevorzugt kontinuierlich, ein- oder mehrstufig erfolgen. In der Regel werden die Polymerisationen bei Temperaturen im Bereich von 20 bis 150°C und Drücken im Bereich von 1 bis 100 bar mit mittleren Verweilzeiten von 0,5 bis 5 Stunden durchgeführt. Bevorzugt sind dabei Temperaturen von 60 bis 90°C, Drücke von 20 bis 35 bar und mittlere Verweilzeiten von 0,5 bis 3 Stunden.The preparation of the components of the propylene polymer composition according to the invention or the entire propylene polymer composition can in a known manner in bulk, in suspension or in the gas phase in the usual, for the polymerization of reactors used either batchwise or preferably continuously, in one or more stages. In the The polymerizations are usually carried out at temperatures in the range of 20 to 150 ° C and pressures in the range of 1 to 100 bar with medium Residence times of 0.5 to 5 hours. Prefers are temperatures from 60 to 90 ° C, pressures from 20 to 35 bar and average residence times of 0.5 to 3 hours.
Hierbei kommen insbesondere in der Polymerisationstechnik übliche Ziegler-Natta-Katalysatorsysteme zum Einsatz. Diese bestehen in der Regel aus einer titanhaltigen Feststoffkomponente, für deren Herstellung neben Titanverbindungen häufig auch anorganische oder polymere feinteilige Träger, Verbindungen des Magnesiums, Halogenverbindungen und Elektronendonorverbindungen eingesetzt werden, und mindestens einem Cokatalysator. Als Cokatalysatoren kommen Aluminiumverbindungen in Betracht. Vorzugsweise werden neben einer Aluminiumverbindung als weitere Cokatalysatoren noch eine oder mehrere Elektronendonorverbindungen eingesetzt.This is particularly common in polymerization technology Ziegler-Natta catalyst systems are used. These consist of usually from a titanium-containing solid component, for the In addition to titanium compounds, they are often also inorganic or polymeric particulate carriers, compounds of magnesium, halogen compounds and electron donor compounds used and at least one cocatalyst. As cocatalysts aluminum compounds come into consideration. Preferably be in addition to an aluminum compound as further cocatalysts one or more electron donor compounds are used.
Zur Herstellung der Propylenpolymerisate können auch Katalysatorsysteme auf Basis von Metallocenverbindungen verwendet werden. Unter Metallocenen sollen hier Komplexverbindungen aus Metallen von Nebengruppen des Periodensystems mit organischen Liganden verstanden werden, die zusammen mit metalloceniumionenbildenden Verbindungen wirksame Katalysatorsysteme ergeben.Catalyst systems can also be used to prepare the propylene polymers based on metallocene compounds. Complex compounds of metals are said to be here under metallocenes of subgroups of the periodic table with organic ligands are understood that together with metallocenium ion-forming Compounds yield effective catalyst systems.
Üblicherweise eingesetzte Metallocene enthalten als Zentralatome Titan, Hafnium oder bevorzugt Zirkonium, wobei im Allgemeinen das Zentralatom über eine π-Bindung an mindestens eine, in der Regel substituierte Cyclopentadienylgruppe gebunden ist. Die Metallocenkomplexe liegen in den Katalysatorsystemen häufig geträgert vor. Weiterhin enthalten die Metallocen-Katalysatorsysteme als metalloceniumionenbildende Verbindungen üblicherweise Alumoxanverbindungen oder starke, neutrale Lewissäuren, ionische Verbindungen mit lewissauren Kationen oder ionische Verbindungen mit Brönsted-Säuren als Kation.Commonly used metallocenes contain as central atoms Titanium, hafnium or preferably zirconium, which generally is Central atom via a π bond to at least one, usually substituted cyclopentadienyl group is bound. The metallocene complexes are often supported in the catalyst systems in front. The metallocene catalyst systems also contain as Metallocenium ion-forming compounds, usually alumoxane compounds or strong, neutral Lewis acids, ionic Compounds with Lewis Acidic Cations or Ionic Compounds with Brönsted acids as a cation.
Die erfindungsgemäße teilkristalline Propylenpolymerisat-Zusammensetzung weist vorzugsweise Molmassen (Gewichtsmittel Mw) zwischen 50 000 und 800 000 g/mol auf. Ihre Schmelze-Fließraten, bei 230°C und unter einem Gewicht von 2,16 kg nach ISO 1133, liegen im Bereich von 0,1 bis 100 g/10 min, vorzugsweise im Bereich von 0,5 bis 50 g/10 min und insbesondere im Bereich von 1 bis 10 g/10 min.The partially crystalline propylene polymer composition according to the invention preferably has molar masses (weight average M w ) between 50,000 and 800,000 g / mol. Their melt flow rates, at 230 ° C and under a weight of 2.16 kg according to ISO 1133, are in the range from 0.1 to 100 g / 10 min, preferably in the range from 0.5 to 50 g / 10 min and especially in the range of 1 to 10 g / 10 min.
Üblicherweise werden der erfindungsgemäßen teilkristallinen Propylenpolymerisat-Zusammensetzung vor der Anwendung übliche Additive wie Stabilisatoren, Gleit- und Entformungsmittel, Füllstoffe, Nukleierungsmittel, Antistatika, Weichmacher, Farbstoffe, Pigmente oder Flammschutzmittel in üblichen Mengen zugesetzt. In der Regel werden diese bei der Granulierung des pulverförmig anfallenden Polymerisationsprodukts in das Polymerisat eingearbeitet.Usually, the partially crystalline propylene polymer composition according to the invention usual additives before use such as stabilizers, lubricants and mold release agents, fillers, Nucleating agents, antistatic agents, plasticizers, dyes, Pigments or flame retardants added in usual amounts. In As a rule, these are obtained when the powder is granulated Polymerization product incorporated into the polymer.
Übliche Stabilisatoren sind Antioxidantien wie sterisch gehinderte Phenole, Verarbeitungsstabilisatoren wie Phosphite oder Phosphonite, Säurefänger wie Calcium- oder Zinkstearat oder Dihydrotalcit, sterisch gehinderte Amine oder auch UV-Stabilisatoren. Im allgemeinen enthält die erfindungsgemäße Propylenpolymerisat-Zusammensetzung einen oder mehrere der Stabilisatoren in Mengen bis zu 2 Gew.-%.Common stabilizers are antioxidants such as sterically hindered ones Phenols, processing stabilizers such as phosphites or Phosphonites, acid scavengers such as calcium or zinc stearate or dihydrotalcite, sterically hindered amines or UV stabilizers. In general, the propylene polymer composition according to the invention contains one or more of the stabilizers in amounts up to 2% by weight.
Geeignete Gleit- und Entformungsmittel sind beispielsweise Fettsäuren, Calcium- oder Zinksalze der Fettsäuren, Fettsäureamide oder niedermolekulare Polyolefinwachse, die üblicherweise in Konzentrationen bis 2 Gew-% eingesetzt werden.Suitable lubricants and mold release agents are, for example, fatty acids, Calcium or zinc salts of fatty acids, fatty acid amides or low molecular weight polyolefin waxes, usually in concentrations up to 2% by weight can be used.
Als Füllstoffe für die Propylenpolymerisat-Zusammensetzung kommen z.B. Talkum, Kreide oder Glasfasern in Betracht, wobei hier Mengen bis 50 Gew.-% verwendet werden können.Coming as fillers for the propylene polymer composition e.g. Talc, chalk or glass fibers are considered, with quantities here up to 50 wt .-% can be used.
Geeignete Nukleierungsmittel sind beispielsweise anorganische
Zusatzstoffe wie Talkum, Kieselsäure oder Kaolin, Salze von Mono-
oder Polycarbonsäuren wie Natriumbenzoat oder Aluminium-tert.-butylbenzoat,
Dibenzylidensorbitol oder dessen C1-C8-alkylsubstituierte
Derivate wie Methyl- oder Dimethyldibenzylidensorbitol oder
Salze von Diestern der Phosphorsäure wie Natrium-2,2'-methylenbis
(4,6,-di-tert.-butylphenyl)phosphat. Der Gehalt der Propylenpolymerisat-Zusammensetzung
an Nukleierungsmitteln beträgt in der
Regel bis 5 Gew.-%.Suitable nucleating agents are, for example, inorganic additives such as talc, silica or kaolin, salts of mono- or polycarboxylic acids such as sodium benzoate or aluminum tert-butylbenzoate, dibenzylidene sorbitol or its C 1 -C 8 -alkyl-substituted derivatives such as methyl or dimethyldibenzylidene sorbitol or salts of diesters Phosphoric acid such as
Solche Additive sind in der Regel handelsüblich und werden beispielsweise in Gächter/Müller, Plastics Additives Handbook, 4th Edition, Hansa Publishers, Munich, 1993 beschrieben.Such additives are usually commercially available and are, for example in Gächter / Müller, Plastics Additives Handbook, 4th Edition, Hansa Publishers, Munich, 1993.
Aufgrund der guten anwendungstechnischen Eigenschaften eignen sich die erfindungsgemäßen teilkristallinen Propylenpolymerisat-Zusammensetzungen vor allem zur Herstellung von Folien, Fasern oder Formkörpern und insbesondere zur Herstellung von biaxial gereckte Folien.Suitable due to the good application properties the partially crystalline propylene polymer compositions according to the invention especially for the production of foils, fibers or moldings and in particular for the production of biaxial stretched foils.
Ein weiterer Gegenstand der Erfindung sind aus den erfindungsgemäßen teilkristallinen Propylenpolymerisat-Zusammensetzungen hergestellte biaxial gereckte Folien mit einem Reckverhältnis von mindestens 1:3 in der Längsrichtung und von mindesten 1:5 in der Querrichtung.Another object of the invention are from the invention Semi-crystalline propylene polymer compositions produced biaxially stretched films with a stretch ratio of at least 1: 3 in the longitudinal direction and at least 1: 5 in the Cross direction.
Die Herstellung der biaxial gereckten Folien kann durch Schmelzeextrusion der Propylenpolymerisat-Zusammensetzung erfolgen, wobei die ausgetragene Schmelze zunächst auf eine Temperatur von 100 bis 20°C abgekühlt wird, um sie zu verfestigen, und der verfestigte Film dann in der Längsrichtung bei einer Temperatur von 80 bis 150°C mit einem Reckverhältnis von mindestens 1:3 und in der Querrichtung bei einer Temperatur von 120 bis 170°C mit einem Reckverhältnis von mindestens 1:5 gereckt wird. The biaxially stretched films can be produced by melt extrusion the propylene polymer composition take place, wherein the melt discharged initially to a temperature of 100 cooled to 20 ° C to solidify them, and the solidified Film then lengthways at a temperature of 80 up to 150 ° C with a stretch ratio of at least 1: 3 and in the Transverse direction at a temperature of 120 to 170 ° C with a Stretching ratio of at least 1: 5 is stretched.
Hierzu schmilzt man die teilkristalline Propylenpolymerisat-Zusammensetzungen bei Temperaturen von beispielsweise 220 bis 300°C, bevorzugt von 240 bis 280°C, in einem Extruder auf, wobei im Extruder weitere Additive oder Polymerisate zugegeben werden können, und extrudiert die Schmelze durch eine Flachdüse oder eine ringförmige Düse.For this purpose, the partially crystalline propylene polymer compositions are melted at temperatures of, for example, 220 to 300 ° C, preferably from 240 to 280 ° C, in an extruder, wherein further additives or polymers are added in the extruder can, and extrudes the melt through a flat die or an annular nozzle.
Zur Verfestigung wird die erhaltene Folie dann abgekühlt. Bei einer Extrusion durch eine Flachdüse (Breitschlitzdüse) erfolgt die Kühlung in der Regel durch eine oder mehrere Abzugswalzen, die eine Oberflächentemperatur von beispielsweise 10 bis 100°C, vorzugsweise 15 bis 70°C, haben. Bei Einsatz einer ringförmigen Düse wird zum Kühlen des Folienschlauchs meist Luft oder Wasser mit einer Temperatur von 0 bis 40°C eingesetzt.The film obtained is then cooled to solidify. At an extrusion through a flat die (slot die) cooling usually by one or more take-off rollers, which have a surface temperature of, for example, 10 to 100 ° C, preferably 15 to 70 ° C. When using an annular The nozzle is usually used to cool the film tube, either air or water used with a temperature of 0 to 40 ° C.
Die erhaltene Folie wird anschließend längs und quer zur Extrusionsrichtung gereckt, was zu einer Orientierung der Molekülketten führt. Die Reihenfolge des Reckens ist nicht kritisch. Bei der Breitschlitzextrusion wird in der Regel zunächst die Längsreckung mit Hilfe von mehreren, entsprechend dem angestrebten Reckverhältnis unterschiedlich schnell laufenden Walzenpaaren durchgeführt. Anschließend erfolgt die Querreckung mittels einer entsprechenden Kluppenvorrichtung. Ebenso kann die Längs- und Querreckung mittels einer geeigneten Kluppenvorrichtung simultan erfolgen. Beim Einsatz einer ringförmigen Düse erfolgt das Recken in der Regel simultan in beide Richtungen durch Einblasen von Gas in den Folienschlauch.The film obtained is then along and across the extrusion direction stretched, leading to an orientation of the molecular chains leads. The order of stretching is not critical. At The slot extrusion is usually the first Longitudinal stretching with the help of several, according to the desired Stretch ratio of roller pairs running at different speeds carried out. The transverse stretching then takes place by means of a corresponding clip device. Likewise, the longitudinal and Transverse stretching simultaneously using a suitable clip device respectively. When using an annular nozzle, stretching is carried out usually simultaneously in both directions by blowing in gas in the film tube.
Vor dem Recken ist es möglich, die Folie auf eine Temperatur von beispielsweise 60 bis 110°C vorzuheizen. Vorzugsweise erfolgt die Längsreckung bei einer Temperatur von 80 bis 150°C, insbesondere 100 bis 130°C, und die Querreckung bei einer Temperatur von 120 bis 190°C, insbesondere 145 bis 180°C. Das Längsreckverhältnis beträgt in der Regel mindestens 1:3, vorzugsweise von 1:4 bis 1:7 und insbesondere von 1:4,5 bis 1:5. Das Querreckverhältnis beträgt in der Regel mindestens 1:5, vorzugsweise von 1:6 bis 1:12 und insbesondere von 1:7 bis 1:10.Before stretching it is possible to bring the film to a temperature of for example, preheat 60 to 110 ° C. This is preferably done Longitudinal stretching at a temperature of 80 to 150 ° C, in particular 100 to 130 ° C, and the transverse stretching at a temperature of 120 to 190 ° C, especially 145 to 180 ° C. The longitudinal stretch ratio is usually at least 1: 3, preferably from 1: 4 to 1: 7 and especially from 1: 4.5 to 1: 5. The transverse stretch ratio is usually at least 1: 5, preferably from 1: 6 to 1:12 and especially from 1: 7 to 1:10.
An die biaxiale Reckung kann sich eine Wämebehandlung zur Thermofixierung anschließen, bei der die Folie etwa 0,1 bis 10 s bei einer Temperatur von 100 bis 160°C gehalten wird. Anschließend wird die Folie in üblicher Weise von einer Aufwickeleinrichtung aufgewickelt. A heat treatment for heat setting can be applied to the biaxial stretching connect in which the film at about 0.1 to 10 s a temperature of 100 to 160 ° C is maintained. Subsequently is the film in the usual way from a winder wound up.
Während oder nach der Herstellung der BOPP-Folie können eine oder beide Oberflächen nach einer der bekannten Methoden corona- oder flammbehandelt werden oder bei Bedarf mit einem Metall wie Aluminium bedampft werden.During or after the production of the BOPP film, one or both surfaces according to one of the known methods corona or be flame treated or if necessary with a metal such as aluminum be steamed.
Es ist auch möglich, daß die erfindungsgemäße teilkristalline Propylenpolymerisat-Zusammensetzung nur eine oder nur einige Schichten einer mehrschichtig aufgebauten biaxial gereckten Folien bilden.It is also possible that the partially crystalline according to the invention Propylene polymer composition only one or only a few Layers of a multilayer biaxially oriented Form foils.
Die aus der erfindungsgemäßen teilkristallinen Propylenpolymerisat-Zusammensetzungen hergestellten biaxial gereckten Folien sind insbesondere hervorragend in der Steifigkeit, der Barrierewirkung und der Transparenz.The from the partially crystalline propylene polymer compositions according to the invention are produced biaxially stretched films especially excellent in stiffness, barrier effect and transparency.
Zur Charakterisierung der Proben wurden folgende Prüfungen durchgeführt:
Mn (Zahlenmittel) < 120 000 g/mol bilden zusammen die Nebenkomponente C.Die Differenz Z quantifiziert gemäß der Formel
M n (number average) <120,000 g / mol together form the secondary component C. The difference Z quantified according to the formula
Mit einem Propylenhomopolymerisat, das kommerziell zur OPP-Folienherstellung eingesetzt wird (Novolen® 1104 K der Targor GmbH), wurde wie in Beispiel 1 eine biaxial gereckte Folie mit ca. 20 µm Dicke hergestellt.With a propylene homopolymer that is used commercially for OPP film production is used (Novolen® 1104 K from Targor GmbH), became a biaxially stretched film as in Example 1 with a thickness of approx. 20 µm.
An dem eingesetzten Novolen® 1104 K wurde eine Schmelztemperatur
von 165,5°C, eine Schmelze-Fließrate von 3,2 g/10 min
und ein bei Raumtemperatur in Xylol löslicher Anteil von 3,2
Gew.-% bestimmt. Durch TREF wurde es in die in Tabelle 2 wiedergegebenen
Fraktionen zerlegt. Die Ausbeute der Fraktionierung
betrug 96,7 Gew-%.
Da die Temperatur (TM/2)+7,5°C der untersuchten Propylenpolymerisat-Zusammensetzung
90,25°C betrug, wurde die erste Fraktion
bei dieser Temperatur eluiert. Die Fraktionen 2 - 5 bei
den Temperaturen 94, 98, 102 und 107°C bilden zusammen die
der Komponente C und die Fraktionen 6 und 7 bei den Temperaturen
bei 112 und 117 die Komponente A. Der Masseanteil der
Fraktion 8 lag unter 1 Gew.-%. Diese Fraktion ist somit Z zuzuordnen.
Es ergab sich also eine Zusammensetzung aus
Die Differenz Z betrug somit 4,0 Gew.-%.The difference Z was thus 4.0% by weight.
Die Folieneigenschaften können der nachfolgenden Tabelle 3 entnommen werden.The film properties can be found in Table 3 below be removed.
Mit einem Propylenhomopolymerisat, das kommerziell zur OPP-Folienherstellung eingesetzt wird (Novolen® NQ 10134 der Targor GmbH), wurde wie in Beispiel 1 eine biaxial gereckte Folie mit ca. 20 µm Dicke hergestellt.With a propylene homopolymer that is used commercially for OPP film production is used (Novolen® NQ 10134 from Targor GmbH), became a biaxially stretched film as in Example 1 with a thickness of approx. 20 µm.
An dem eingesetzten Novolen® NQ 10134 wurde eine Schmelztemperatur von 163,1°C, eine Schmelze-Fließrate von 3,4 g/10 min und ein bei Raumtemperatur in Xylol löslicher Anteil von 3,5 Gew.-% bestimmt. Durch TREF wurde es in Fraktionen zerlegt. Die Ausbeute der Fraktionierung lag bei 97,2 Gew-%.A melting temperature was reached on the Novolen® NQ 10134 used of 163.1 ° C, a melt flow rate of 3.4 g / 10 min and a portion of xylene soluble at room temperature 3.5 wt .-% determined. It was broken down into fractions by TREF. The yield of the fractionation was 97.2% by weight.
Es ergab sich eine Zusammensetzung aus
Die Differenz Z betrug somit 2,8 Gew.-%.The difference Z was thus 2.8% by weight.
Das maximale Verhältnis Mw/Mn der die Komponente A bildenden Fraktionen lag bei 2,5.The maximum ratio M w / M n of the fractions forming component A was 2.5.
Mit einem einem statistisch aufgebauten Propylen-Ethylen-Copolymerisat, das kommerziell zur OPP-Folienherstellung eingesetzt wird (Novolen® NX 10094 der Targor GmbH), wurde wie in Beispiel 1 eine biaxial gereckte Folie mit ca. 20 µm Dicke hergestellt.With a statistically constructed propylene-ethylene copolymer, which is used commercially for OPP film production (Novolen® NX 10094 from Targor GmbH), was like in Example 1 a biaxially stretched film with a thickness of about 20 µm manufactured.
An dem eingesetzten Novolen® NX 10094 wurde eine Schmelztemperatur von 155,7°C, eine Schmelze-Fließrate von 2,9 g/10 min, ein bei Raumtemperatur in Xylol löslicher Anteil von 1,7 Gew.-% und ein Ethylen-Gehalt von 1,1 Gew.-% bestimmt. Durch TREF wurde es in die Fraktionen zerlegt. Die Ausbeute der Fraktionierung lag bei 99,7 Gew-%.A melting temperature was set on the Novolen® NX 10094 used of 155.7 ° C, a melt flow rate of 2.9 g / 10 min, a portion soluble in xylene at room temperature of 1.7 wt .-% and an ethylene content of 1.1 wt .-% determined. It was broken down into fractions by TREF. The The yield of the fractionation was 99.7% by weight.
Es ergab sich eine Zusammensetzung aus
Die Differenz Z betrug somit 0,3 Gew.-%.The difference Z was thus 0.3% by weight.
Das maximale Verhältnis Mw/Mn der die Komponente A bildenden Fraktionen lag bei 2,8.The maximum ratio M w / M n of the fractions forming component A was 2.8.
In der nachstehenden Tabelle 3 sind die Eigenschaften der biaxial
gereckten Folien zusammengestellt, die aus den beispielhaft hergestellten
teilkristallinen Propylenpolymerisat-Zusammensetzungen
gefertigt wurden.
Bei dem Vergleich der Beispiele und Vergleichsbeispiele wird ersichtlich, daß die Propylenpolymerisat-Zusammensetzung von Beispiele 1 insbesondere eine breitere Molmassenverteilung, d.h. ein erhöhtes Verhältnis Mw/Mn, in der Hauptkomponente A aufweist und die Propylenpolymerisat-Zusammensetzung von Beispiel 2 einen erhöhten Anteil an Nebenkomponente B besitzt.A comparison of the examples and comparative examples shows that the propylene polymer composition of example 1 in particular has a broader molecular weight distribution, ie an increased ratio M w / M n , in the main component A and the propylene polymer composition of example 2 has an increased proportion Minor component B has.
Der Vergleich zwischen Beispiel 2 und Vergleichsbeispiel C zeigt, daß nicht allein durch Einbau von Ethylen eine erfindungsgemäße Zusammensetzungsverteilung der Propylenpolymerisat-Zusammensetzungen erreicht werden kann. Dies erkennt man auch daran, daß der Einbau von 1,1 Gew.% Ethylen in Vergleichsbeispiel C zu einer Absenkung der Schmelztemperatur auf 155,7°C führt, während in Beispiel 2 trotz eines Gehalts von 1,5 Gew.% Ethylen die Schmelztemperatur auf 163,2°C gehalten werden kann.The comparison between Example 2 and Comparative Example C shows that not only by incorporating ethylene an inventive Composition distribution of the propylene polymer compositions can be achieved. This can also be seen from the fact that the Incorporation of 1.1% by weight of ethylene in comparative example C to reduce it the melting temperature leads to 155.7 ° C, while in example 2 despite a content of 1.5% by weight of ethylene, the melting temperature can be kept at 163.2 ° C.
Tabelle 3 kann entnommen werden, daß mit der Propylenpolymerisat-Zusammensetzung von Beispiele 1 insbesondere bessere mechanische Eigenschaften ohne ein Verlust an Verarbeitbarkeit erhalten werden können. Außerdem sind die Barriereeigenschaften verbessert (geringere Permeabilität von Wasserdampf und Sauerstoff). Die Propylenpolymerisat-Zusammensetzung von Beispiel 2 weist eine bessere Verarbeitbarkeit und bessere optische Eigenschaften (geringere Trübung) auf, ohne daß man Einbußen in den mechanischen Eigenschaften der Folien oder den Barriereeigenschaften in Kauf nehmen muß.Table 3 shows that the propylene polymer composition of examples 1 in particular better mechanical Properties can be obtained without loss of workability can. The barrier properties are also improved (lower permeability of water vapor and oxygen). The Propylene polymer composition of Example 2 has one better processability and better optical properties (lower Turbidity) without sacrificing mechanical Properties of the films or the barrier properties in purchase must take.
Claims (10)
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DE19962130 | 1999-12-21 | ||
DE19962130A DE19962130A1 (en) | 1999-12-21 | 1999-12-21 | Semi-crystalline propylene polymer compositions with good suitability for the production of biaxially oriented films |
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EP1110976A1 true EP1110976A1 (en) | 2001-06-27 |
EP1110976B1 EP1110976B1 (en) | 2006-06-14 |
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US (1) | US6593442B2 (en) |
EP (1) | EP1110976B1 (en) |
JP (1) | JP2001247729A (en) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2002051912A1 (en) * | 2000-12-22 | 2002-07-04 | Basell Poliolefine Italia S.P.A. | Polyolefin sheets for thermoforming |
WO2004011507A1 (en) * | 2002-07-24 | 2004-02-05 | Basell Polyolefine Gmbh | At least two-stage process for preparing propylene polymer compositions |
EP2295478A3 (en) * | 2007-05-22 | 2011-09-07 | Borealis Technology Oy | Polypropylene copolymer |
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JP2002294010A (en) * | 2001-03-30 | 2002-10-09 | Sumitomo Chem Co Ltd | Polypropylene-based resin composition for oriented film and the resultant oriented film |
ES2236090T3 (en) * | 2001-06-27 | 2005-07-16 | Borealis Technology Oy | PROPYLENE POLYMER RESIN WITH IMPROVED PROPERTIES. |
AU2003245926B2 (en) * | 2002-06-12 | 2007-11-29 | Basell Polyolefine Gmbh | Propylene copolymer compositions having a good low-temperature impact toughness and a high transparency |
AU2003242656B2 (en) * | 2002-06-12 | 2008-04-03 | Basell Polyolefine Gmbh | Flexible propylene copolymer compositions having a high transparency |
US7294681B2 (en) | 2002-10-15 | 2007-11-13 | Exxonmobil Chemical Patents Inc. | Mutliple catalyst system for olefin polymerization and polymers produced therefrom |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
US6995213B2 (en) * | 2003-09-29 | 2006-02-07 | Fina Technology, Inc. | Oriented films prepared using impact copolymer polypropylene |
US7217772B2 (en) * | 2005-03-25 | 2007-05-15 | Sunoco, Inc. (R&M) | Process for production of propylene homopolymers |
FR2994510B1 (en) * | 2012-08-09 | 2014-08-08 | Renault Sa | PROCESS FOR THE PREPARATION OF PARTIALLY SURFACE-PROTECTED ACTIVE MATERIALS FOR LITHIUM BATTERIES |
JP2022083825A (en) | 2020-11-25 | 2022-06-06 | 住友化学株式会社 | Propylene polymer composition and film |
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-
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- 2000-12-18 EP EP00127654A patent/EP1110976B1/en not_active Expired - Lifetime
- 2000-12-18 US US09/737,848 patent/US6593442B2/en not_active Expired - Lifetime
- 2000-12-18 AT AT00127654T patent/ATE329942T1/en active
- 2000-12-18 DE DE50012976T patent/DE50012976D1/en not_active Expired - Lifetime
- 2000-12-21 JP JP2000387995A patent/JP2001247729A/en active Pending
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DE50012976D1 (en) | 2006-07-27 |
ATE329942T1 (en) | 2006-07-15 |
US20010004662A1 (en) | 2001-06-21 |
JP2001247729A (en) | 2001-09-11 |
EP1110976B1 (en) | 2006-06-14 |
DE19962130A1 (en) | 2001-07-05 |
US6593442B2 (en) | 2003-07-15 |
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